De nos jours, la contamination des sols par les polluants organiques et inorganiques est une problématique majeure. Des techniques douces de remédiation, reposant sur l’utilisation de plantes et de microorganismes, associés à des amendements ou non, sont étudiées pour gérer ces sols. Parmi les différents amendements, le biochar est présenté dans la littérature comme pouvant répondre à ces attentes. Ce travail se propose d’évaluer l’impact des paramètres de pyrolyse sur les caractéristiques de huit biochars élaborés à partir de Miscanthus x giganteus, cultivé sur un sol contaminé en métaux, et de sélectionner le(s) biochar(s) susceptible(s) d’être le(s) plus performant(s) en termes de remédiation de sols contaminés en métaux (Cd, Pb, Zn) et/ou HAP. Il a été mis en évidence une forte influence de la température de pyrolyse sur les caractéristiques des biochars. De plus, les biochars ont présenté de fortes capacités de sorption des trois métaux et des HAP en solution, notamment pour les biochars produits à 600°C. Des expérimentations réalisées avec un sol artificiel et une terre agricole contaminés artificiellement ont mis en évidence la capacité de certains biochars à diminuer la disponibilité environnementale, la biodisponibilité et la bioaccessibilité orale des métaux et des HAP. Sur la base des résultats obtenus, un biochar a été sélectionné comme répondant le mieux aux attentes en termes de gestion de sols multicontaminés. Compte tenu des modifications structurelles du biochar dans les sols, il conviendrait de valider ces résultats sur le long terme, en condition in situ, tout en s’assurant de l’innocuité du biochar étudié et en intégrant les aspects socio-économiques. / Nowadays, soil contamination by the organic and inorganic pollutants represent a major issue. Gentle remediation options, comprising plants and microorganisms, and linked with the use of amendments or not, are implemented to manage these soils. Among the different amendments, the biochar is presented in the literature as being able to meet these expectations. This study aims at evaluating the impacts of pyrolysis parameters on the characteristics of eight biochars derived from Miscanthus x giganteus, grown on metal contaminated soils, and selecting the one which may be the most efficient to remediate metals (Cd, Pb, Zn) and/or PAHs contaminated soils. A strong influence of pyrolysis temperature on biochar characteristics was detected. Moreover, biochars showed strong sorption capacity for the three metals and PAHs in aqueous solution, especially for those produced at 600°C. Experiments realized with an artificial soil, and an agricultural soil, both artificially contaminated, demonstrated the efficiency of some biochars to decrease the environmental availability, bioavailability and oral bioaccessibility of the metals and PAHs. Based on the results, one biochar was selected as being the most efficient to manage the contaminated soils. In view of the structural modifications of biochars in soils, these results should be validated in situ on long term basis, while ensuring the harmless effects of the studied biochar and integrating the socio-economic aspects.

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Made available in DSpace on 2018-08-01T22:33:09Z (GMT). No. of bitstreams: 1 tese_8995_Cristiane Francisca Barbosa.pdf: 1390114 bytes, checksum: 618f0bde8a50c7e3ee2bedb6b6c10580 (MD5) Previous issue date: 2016-08-31 / Biocarvão é o produto da decomposição térmica de materiais orgânicos sob baixa concentração de oxigênio e em temperaturas controladas. Os benefícios agronômicos e ambientais do seu uso estão associados a temperatura de pirólise e a matéria prima utilizada para o seu processamento. Este estudo teve por objetivo avaliar a influência da matéria prima e da temperatura de pirólise na caracterização final do produto e nas alterações de suas características químicas e físicas. Para isso, os biocarvões foram provenientes de duas temperaturas (350 °C e 600 °C) e dois resíduos (palha de café - PC e casca de eucalipto - CE). O processo de pirólise lenta foi realizado em um reator metálico de leito fixo hermeticamente fechado, com tempo de permanência do material na temperatura final de 60 minutos. Os rendimentos em biocarvão, bio-óleo e gases foram quantificados e nos biocarvões foram determinados: os teores elementares de carbono (C), hidrogênio (H), nitrogênio (N) e oxigênio (O), pH, capacidade de troca catiônica (CTC), teor de cinzas (Cz) e de nutrientes (Ca, Mg, K e P). As mudanças morfológicas decorrentes do processo de pirólise foram investigadas por microscopia eletrônica de varredura (MEV). Determinou-se a densidade aparente (Da) pelo método da proveta, e a capacidade de retenção de água dos biocarvões a (- 33kPa) em extrator de placa porosa. Os resultados experimentais mostraram que a pirólise da CE a temperatura de 350 °C proporcionou maior rendimento em biocarvão. O tipo de matéria prima não influenciou os teores de C dos biocarvões, apenas os teores de H, O e N. Biocarvões obtidos da PC apresentaram maiores teores de Mg, P e K, maior CTC e pH mais alcalino. Biocarvões de CE apresentaram maiores teores de Ca e cinzas. A pirólise a 600 °C obteve biocarvões com maior relação C/N, menores teores de H, N e O, menor CTC, maior teor de cinzas e nutrientes, pH mais alcalino e maior aromaticidade. A análise de espectroscopia de Infravermelho por Transformada de Fourier (FTIR) evidenciou uma diminuição de grupos funcionais e aumento de grupos aromáticos com a elevação da temperatura. As micrografias de MEV demonstraram que os biocarvões obtidos a 600 °C apresentaram poros mais desenvolvidos, com menor espessura da parede e maior desarranjo estrutural. A densidade dos biocarvões variou em função da matéria prima utilizada, os biocarvões de CE apresentaram maior densidade, em relação aos de PC.

Water pollution is one of the major ecological threats people face around the world. Water contamination by organic and inorganic compounds is hazardous to both the environment and human health. Adsorption techniques have gained much attention in the field of water remediation due to their efficiency, simplicity in operation, and ease of implementation. However, the adsorbents currently being used are costly. The main objective of this work is to develop novel, low-cost adsorbents from waste material by modifying the adsorbent surface for water remediation. Adsorbent modifications involve various chemical and physical methods such as acid/base treatments, metal/metal oxide impregnation, functional group alteration, and steam/air activation. In chapter I, these modification methods are summarized along with characterization techniques and adsorption interactions available for contaminant removal. In chapter II, a novel activated carbon is introduced from the fruit of Garcinia cambogia with acid activation, for the removal of Pb(II) and Cd(II) from water. Activated carbon was prepared by soaking dried Garcinia cambogia pieces in 85% phosphoric acid and carbonizing at 650 °C in a muffle furnace for 1 h. Chapter III describes the modification of waste tire rubber as an adsorbent for heavy metal ion removal. This modification was done by mixing ground tire rubber (GTR) with chitosan dissolved acetic acid (2%) solution followed by NaOH treatment. Chitosan modified-GTR successfully removed more Pb(II) and Cu(II) ions than GTR, suggesting added amine groups on the GTR surface through chitosan modification enhanced the heavy metal ion adsorption. In chapter IV, caffeine, ibuprofen, and acetylsalicylic acid removals by hybrid magnetic Fe3O4/Douglas fir biochar adsorbent are discussed. Adsorptions were compared with non-magnetic Douglas fir biochar. The surface chemistry and composition of modified adsorbents were examined by SEM, SEM-EDX, TEM, PZC, XRD, XPS, FTIR, TGA, elemental analysis, and surface area measurements.

Soil biochar application effects in agricultural systems are not well understood. Corn (Zea mays L.), soybean (Glycine max L.), wheat (Triticum aestivum L.), cereal rye (Secale cereal L.), and alfalfa (Medicago sativa L.) were grown on two soils amended with four rates of biochar, a Marietta fine sandy loam (fine-loamy, siliceous, active, thermic Fluvaaquentic Eutrudept) and a Houston silty clay (very fine, smectitic, thermic Oxyaquic Haplaudert) and allowed to equilibrate for 56 days. To investigate a possible nitrogen effect, three nitrogen rates were added to non-legume species. Our results revealed reductions in nutrient uptake across all crops, but this followed the same trend as shoot dry weight production and plant tissue concentration for pots treated with biochar. The significant reduction in uptake and tissue concentration are believed to be linked to smaller plant sizes. Therefore, it is believed that biochar applications are not having an effect on plant growth.

Little is known about the effect of biochar created from poultry litter on soil properties and plant growth. Five studies were conducted using biochar made by the fast pyrolysis of poultry litter. Two were greenhouse studies and three were field studies. The greenhouse studies were conducted with a sandy loam soil and a silt loam soil. First, lettuce (Lactuca sativa L) seeds were germinated in the greenhouse across biochar incorporation rates from 0 to 100%, and secondly a trial was conducted in which green peppers (capsicum annum L) were grown in soils with up to 5% biochar by weight. Elemental analysis was completed on the biochar and the soils were analyzed for bulk density (BD), water holding capacity (WHC), pH, cation exchange capacity (CEC), soluble salts (SS) and extractable nutrients. The field studies all used the rates of 0, 4.5, and 9 Mg ha-1 biochar and the rates were applied in the early spring of 2009 and 2010. Biochar was surface applied on a tall fescue pasture [Lolium arundinaceum (Schreb.) Darbysh. (=Festuca arundinacea Schreb. subsp. arundinacea)] and tilled in on two green pepper field sites. The soils were analyzed for carbon (C) content, pH, CEC, Mehlich 1 P, and SS. No significant difference was found in yields at any of the three sites, but differences in forage quality were found. Biochar made from poultry litter showed several benefits as a soil amendment in all the studies, but application rates would be limited by soil test P and pH. / Master of Science

A aplicação de biocarvão ao solo tem sido divulgada como prática com vantagens agrícolas e ambientais. Devido à sua elevada reatividade, o biocarvão pode interagir com contaminantes orgânicos e inorgânicos do solo, diminuindo o potencial poluidor de elementos tóxicos e pesticidas. Contudo, a eficácia de herbicidas pré-emergentes pode ser anulada devido à presença de biocarvão no solo, o que impõe a necessidade de doses maiores e resulta no aumento do risco de contaminação ambiental. Adicionalmente, pode haver maior persistência de pesticidas no solo devido à retenção e menor disponibilidade das moléculas em solos com biocarvão. As reações que ocorrem entre o biocarvão e os pesticidas dependem das próprias características do solo e da molécula, além do tempo de interação com o solo (aging) e das propriedades intrínsecas ao biocarvão (biomassa de origem, T°C de pirólise e granulometria). O tebuthiuron e a hexazinona são herbicidas com elevado potencial de lixiviação e podem ter seu destino alterado em função da presença de biocarvão no solo. Estas moléculas possuem elevado tempo de meia-vida (t1/2) e biodegradam lentamente no ambiente edáfico. Assim, processos oxidativos avançados (POA) podem acelerar a decomposição dos herbicidas, sendo ainda uma maneira de integrar o biocarvão em processos químicos para a dissipação de poluentes. Objetivou-se avaliar os efeitos da aplicação de biocarvão na dinâmica dos herbicidas tebuthiuron e hexazinona em solos, tendo-se como objetivos específicos: i) verificar o comportamento sortivo desses herbicidas frente à aplicação de biocarvões produzidos a partir de diferentes matérias-primas e T°C de pirólise, incluindo a influência de fatores como o aging dos herbicidas no solo, tamanho das partículas do biocarvão e disponibilidade de carbono orgânico dissolvido (COD) no solo promovida pela adição do biocarvão; ii) avaliar se a interação entre os herbicidas e o biocarvão afeta a eficiência de controle de braquiária (Brachiaria decumbens); iii) analisar a influência do biocarvão na dissipação e lixiviação de tebuthiuron e hexazinona; e iv) identificar o potencial de uso do biocarvão em POA, como suporte para catalisadores metálicos heterogêneos e como fonte de ferro para reações de Fenton, bem como avaliar o desempenho destes materiais na catálise oxidativa de hidrocarbonetos e dos herbicidas. Experimentos de sorção, (verificando a influência de biocarvões de diferentes matérias-primas e T°C de pirólise, aging e granulometria, além da avaliação em solos de texturas contrastantes), bem como de dissipação e lixiviação foram conduzidos, utilizando-se herbicidas radiomarcados. Em paralelo, a liberação de COD pelos biocarvões e pelos solos foi quantificada, enquanto que um experimento de eficiência de controle sobre braquiária em casa de vegetação foi conduzido. Os biocarvões foram, ainda, avaliados quanto ao potencial de uso como suporte para catalisadores metálicos e para reações de Fenton, avaliando-se sua performance para a oxidação dos herbicidas e de hidrocarbonetos. Apesar de não alterar a classe de lixiviação de tebuthiuron e hexazinona em curto prazo, quando considerado o efeito do aging, a presença de biocarvão de palha de cana-de-açúcar 550°C (PC550) no solo, independentemente da granulometria, pode auxiliar no manejo de herbicidas com elevada mobilidade, especialmente em solos de textura arenosa e com baixo teor de carbono. Neste caso, o herbicida tebuthiuron teve sua classificação alterada de \"molécula lixiviável\" (Kd,app < 5,0 L kg-1) para \"molécula não-lixiviável\" (Kd,app > 5,0 L kg-1). No entanto, o biocarvão de dejeto de galinha 350°C (DG350) aumenta o COD do solo, resultando na diminuição da sorção dos herbicidas. A adição dos biocarvões PC550 e DG350 ao solo não modificam a eficiência de controle de braquiária por moléculas altamente solúveis. Doses a partir das doses recomendadas em campo promovem controle eficiente, independentemente da presença ou não de biocarvão no solo. Tebuthiuron e hexazinona são moléculas recalcitrantes no ambiente, sendo muito baixas suas taxas de mineralização e de dissipação, tanto na presença como na ausência dos biocarvões PC550 e DG350. A presença de biocarvão no solo pouco influenciou a dissipação dessas moléculas. Os biocarvões PC550 e DG350 diminuem o potencial de lixiviação da hexazinona no solo de textura areia franca, mas não afetam o movimento vertical do tebuthiuron nas mesmas condições. Apesar do menor potencial para degradação de tebuthiuron e hexazinona em relação à epoxidação de hidrocarbonetos, a inserção do biocarvão para a síntese de catalisadores mostrou-se eficiente e permitiu o emprego deste material em processos de catálise industrial e ambiental, podendo auxiliar para o manejo da remediação de poluentes e contribuindo para expandir o uso do biocarvão. / Biochar amendments to soil has been claimed as a practice with agricultural and environmental advantages. Due to its high reactivity, biochar can interact with organic and inorganic soil contaminants, reducing the pollution potential of toxic elements and pesticides. However, pre-emergent herbicides efficacy can be negatively affected by biochar additions to the soil, which may impose higher doses and increase the environmental contamination risk. In addition, there may be increasing in the pesticide\'s persistence due to retention and lower availability of the molecules induced by biochar amendment to the soil. The interactions between biochar and the pesticides depend on the characteristics of the soil and the herbicide itself, besides the aging and the biochar\'s properties (biomass, pyrolysis T°C and granulometry). Tebuthiuron and hexazinone are herbicides with leaching potential and may have their fate modified due to the presence of biochar in the soil. These molecules have a high half-life time (t1/2) and biodegrade slowly in the environment. Thus, advanced oxidative processes (AOP) can accelerate the decomposition of herbicides and can be a way of incorporate biochar in chemical processes towards pollutants dissipation. We aimed to evaluate the effects of biochar amendments on tebuthiuron and hexazinone dynamics in soils, and the specific objectives were: i) to verify the sorption behavior of these herbicides in response to biochar\'s amendment from different feedstock and pyrolysis T°C, including the influence of factors such as herbicide aging on the soil, biochar particle size and availability of dissolved organic carbon (DOC) in the soil promoted by biochar addition; ii) to evaluate if the interaction between the herbicides and the biochars affects braquiária (Brachiaria decumbens) control efficiency; iii) to analyze the biochars influence on the dissipation and leaching of tebuthiuron and hexazinone; and iv) to identify the potential use of biochar in AOP as heterogeneous metal catalysts support and as a source of iron for Fenton reactions, as well as to evaluate the performance of these materials in oxidative catalysis of hydrocarbons and herbicides. Sorption experiments, (checking the influence of biochars from different feedstocks and pyrolysis T°C, aging and granulometry, as well as accessing the differences among soil textures), and dissipation and leaching experiments were conducted using radiolabeled herbicides. In parallel, the release of DOC by the biochars and soils was quantified, whereas an experiment in a greenhouse for braquiária control was conducted. The biochars were also evaluated for use as metal catalysts supports and for Fenton reactions, evaluating their performance for herbicides and hydrocarbons oxidation. Although it does not change tebuthiuron and hexazinone leaching class in short term, when considering the aging, the sugarcane straw biochar pyrolyzed at 550°C (PC550), regardless of granulometry, may be useful in the management of high mobility herbicides, especially in sandy soils with low carbon content. In this case, tebuthiuron had its classification modified from \"leachable\" (Kd,app < 5.0 L kg-1) for \"non-leachable\" molecule (Kd,app > 5.0 L kg-1). However, the biochar from poultry manure pyrolyzed at 350°C (DG350) increases the DOC content in the soil, resulting in decreased sorption of the herbicides. The additions of PC550 and DG350 to the soil does not modify the control efficiency of braquiária by highly soluble molecules. Doses higher than the recommended ones promote efficient control, regardless of the presence or absence of biochar in the soil. Tebuthiuron and hexazinone are highly recalcitrant molecules in the environment, having low rates of mineralization and dissipation both in the presence or absence of the biochars PC550 and DG350. The biochar application to the soil barely influenced the herbicides dissipation. The biochars PC550 and DG350 decrease the leaching potential of hexazinone in the sandy soil, but do not affect tebuthiuron leaching in the same conditions. Despite the lower potential for tebuthiuron and hexazinone degradation in relation to the epoxidation of hydrocarbons potential, biochar insertion in the synthesis of catalysts has been proved to be efficient, allowing the use of these wastes in industrial and environmental catalysis processes for pollutants remediation purposes and helping to expand the biochar range of uses.

A aplicação de biocarvão ao solo tem sido divulgada como prática com vantagens agrícolas e ambientais. Devido à sua elevada reatividade, o biocarvão pode interagir com contaminantes orgânicos e inorgânicos do solo, diminuindo o potencial poluidor de elementos tóxicos e pesticidas. Contudo, a eficácia de herbicidas pré-emergentes pode ser anulada devido à presença de biocarvão no solo, o que impõe a necessidade de doses maiores e resulta no aumento do risco de contaminação ambiental. Adicionalmente, pode haver maior persistência de pesticidas no solo devido à retenção e menor disponibilidade das moléculas em solos com biocarvão. As reações que ocorrem entre o biocarvão e os pesticidas dependem das próprias características do solo e da molécula, além do tempo de interação com o solo (aging) e das propriedades intrínsecas ao biocarvão (biomassa de origem, T°C de pirólise e granulometria). O tebuthiuron e a hexazinona são herbicidas com elevado potencial de lixiviação e podem ter seu destino alterado em função da presença de biocarvão no solo. Estas moléculas possuem elevado tempo de meia-vida (t1/2) e biodegradam lentamente no ambiente edáfico. Assim, processos oxidativos avançados (POA) podem acelerar a decomposição dos herbicidas, sendo ainda uma maneira de integrar o biocarvão em processos químicos para a dissipação de poluentes. Objetivou-se avaliar os efeitos da aplicação de biocarvão na dinâmica dos herbicidas tebuthiuron e hexazinona em solos, tendo-se como objetivos específicos: i) verificar o comportamento sortivo desses herbicidas frente à aplicação de biocarvões produzidos a partir de diferentes matérias-primas e T°C de pirólise, incluindo a influência de fatores como o aging dos herbicidas no solo, tamanho das partículas do biocarvão e disponibilidade de carbono orgânico dissolvido (COD) no solo promovida pela adição do biocarvão; ii) avaliar se a interação entre os herbicidas e o biocarvão afeta a eficiência de controle de braquiária (Brachiaria decumbens); iii) analisar a influência do biocarvão na dissipação e lixiviação de tebuthiuron e hexazinona; e iv) identificar o potencial de uso do biocarvão em POA, como suporte para catalisadores metálicos heterogêneos e como fonte de ferro para reações de Fenton, bem como avaliar o desempenho destes materiais na catálise oxidativa de hidrocarbonetos e dos herbicidas. Experimentos de sorção, (verificando a influência de biocarvões de diferentes matérias-primas e T°C de pirólise, aging e granulometria, além da avaliação em solos de texturas contrastantes), bem como de dissipação e lixiviação foram conduzidos, utilizando-se herbicidas radiomarcados. Em paralelo, a liberação de COD pelos biocarvões e pelos solos foi quantificada, enquanto que um experimento de eficiência de controle sobre braquiária em casa de vegetação foi conduzido. Os biocarvões foram, ainda, avaliados quanto ao potencial de uso como suporte para catalisadores metálicos e para reações de Fenton, avaliando-se sua performance para a oxidação dos herbicidas e de hidrocarbonetos. Apesar de não alterar a classe de lixiviação de tebuthiuron e hexazinona em curto prazo, quando considerado o efeito do aging, a presença de biocarvão de palha de cana-de-açúcar 550°C (PC550) no solo, independentemente da granulometria, pode auxiliar no manejo de herbicidas com elevada mobilidade, especialmente em solos de textura arenosa e com baixo teor de carbono. Neste caso, o herbicida tebuthiuron teve sua classificação alterada de \"molécula lixiviável\" (Kd,app < 5,0 L kg-1) para \"molécula não-lixiviável\" (Kd,app > 5,0 L kg-1). No entanto, o biocarvão de dejeto de galinha 350°C (DG350) aumenta o COD do solo, resultando na diminuição da sorção dos herbicidas. A adição dos biocarvões PC550 e DG350 ao solo não modificam a eficiência de controle de braquiária por moléculas altamente solúveis. Doses a partir das doses recomendadas em campo promovem controle eficiente, independentemente da presença ou não de biocarvão no solo. Tebuthiuron e hexazinona são moléculas recalcitrantes no ambiente, sendo muito baixas suas taxas de mineralização e de dissipação, tanto na presença como na ausência dos biocarvões PC550 e DG350. A presença de biocarvão no solo pouco influenciou a dissipação dessas moléculas. Os biocarvões PC550 e DG350 diminuem o potencial de lixiviação da hexazinona no solo de textura areia franca, mas não afetam o movimento vertical do tebuthiuron nas mesmas condições. Apesar do menor potencial para degradação de tebuthiuron e hexazinona em relação à epoxidação de hidrocarbonetos, a inserção do biocarvão para a síntese de catalisadores mostrou-se eficiente e permitiu o emprego deste material em processos de catálise industrial e ambiental, podendo auxiliar para o manejo da remediação de poluentes e contribuindo para expandir o uso do biocarvão. / Biochar amendments to soil has been claimed as a practice with agricultural and environmental advantages. Due to its high reactivity, biochar can interact with organic and inorganic soil contaminants, reducing the pollution potential of toxic elements and pesticides. However, pre-emergent herbicides efficacy can be negatively affected by biochar additions to the soil, which may impose higher doses and increase the environmental contamination risk. In addition, there may be increasing in the pesticide\'s persistence due to retention and lower availability of the molecules induced by biochar amendment to the soil. The interactions between biochar and the pesticides depend on the characteristics of the soil and the herbicide itself, besides the aging and the biochar\'s properties (biomass, pyrolysis T°C and granulometry). Tebuthiuron and hexazinone are herbicides with leaching potential and may have their fate modified due to the presence of biochar in the soil. These molecules have a high half-life time (t1/2) and biodegrade slowly in the environment. Thus, advanced oxidative processes (AOP) can accelerate the decomposition of herbicides and can be a way of incorporate biochar in chemical processes towards pollutants dissipation. We aimed to evaluate the effects of biochar amendments on tebuthiuron and hexazinone dynamics in soils, and the specific objectives were: i) to verify the sorption behavior of these herbicides in response to biochar\'s amendment from different feedstock and pyrolysis T°C, including the influence of factors such as herbicide aging on the soil, biochar particle size and availability of dissolved organic carbon (DOC) in the soil promoted by biochar addition; ii) to evaluate if the interaction between the herbicides and the biochars affects braquiária (Brachiaria decumbens) control efficiency; iii) to analyze the biochars influence on the dissipation and leaching of tebuthiuron and hexazinone; and iv) to identify the potential use of biochar in AOP as heterogeneous metal catalysts support and as a source of iron for Fenton reactions, as well as to evaluate the performance of these materials in oxidative catalysis of hydrocarbons and herbicides. Sorption experiments, (checking the influence of biochars from different feedstocks and pyrolysis T°C, aging and granulometry, as well as accessing the differences among soil textures), and dissipation and leaching experiments were conducted using radiolabeled herbicides. In parallel, the release of DOC by the biochars and soils was quantified, whereas an experiment in a greenhouse for braquiária control was conducted. The biochars were also evaluated for use as metal catalysts supports and for Fenton reactions, evaluating their performance for herbicides and hydrocarbons oxidation. Although it does not change tebuthiuron and hexazinone leaching class in short term, when considering the aging, the sugarcane straw biochar pyrolyzed at 550°C (PC550), regardless of granulometry, may be useful in the management of high mobility herbicides, especially in sandy soils with low carbon content. In this case, tebuthiuron had its classification modified from \"leachable\" (Kd,app < 5.0 L kg-1) for \"non-leachable\" molecule (Kd,app > 5.0 L kg-1). However, the biochar from poultry manure pyrolyzed at 350°C (DG350) increases the DOC content in the soil, resulting in decreased sorption of the herbicides. The additions of PC550 and DG350 to the soil does not modify the control efficiency of braquiária by highly soluble molecules. Doses higher than the recommended ones promote efficient control, regardless of the presence or absence of biochar in the soil. Tebuthiuron and hexazinone are highly recalcitrant molecules in the environment, having low rates of mineralization and dissipation both in the presence or absence of the biochars PC550 and DG350. The biochar application to the soil barely influenced the herbicides dissipation. The biochars PC550 and DG350 decrease the leaching potential of hexazinone in the sandy soil, but do not affect tebuthiuron leaching in the same conditions. Despite the lower potential for tebuthiuron and hexazinone degradation in relation to the epoxidation of hydrocarbons potential, biochar insertion in the synthesis of catalysts has been proved to be efficient, allowing the use of these wastes in industrial and environmental catalysis processes for pollutants remediation purposes and helping to expand the biochar range of uses.

Το στράγγισμα από τους χώρους υγειονομικής ταφής απορριμμάτων (ΧΥΤΑ) περιέχει σύνθετους οργανικούς ρύπους, με αποτέλεσμα η επεξεργασία του να έχει αποκτήσει ιδιαίτερη σημασία στις μέρες μας. Εκτός από τις μεγάλες ποσότητες οργανικού υλικού μέσα στα στραγγίσματα υπάρχουν επίσης βαρέα μέταλλα, χλωριωμένα οργανικά ή ανόργανα άλατα και γενικά διάφορες ουσίες που μπορεί να ρυπάνουν τα επιφανειακά και υπόγεια νερά. Γι ‘ αυτό κατά την κατασκευή ενός ΧΥΤΑ πρέπει να εγκατασταθούν συστήματα συλλογής και επεξεργασίας των στραγγισμάτων, ώστε να αποφευχθεί το φιλτράρισμα τους μέσω του εδάφους και τους υπεδάφους και στη συνέχεια η περαιτέρω μόλυνση ρεμάτων ή γεωτρήσεων. Στην παρούσα εργασία θα ασχοληθούμε συγκεκριμένα με τον χαρακτηρισμό των στραγγισμάτων όσον αφορά το χημικά απαιτούμενο οξυγόνο (COD), το βιοχημικά απαιτούμενο οξυγόνο (BOD), τα συνολικά αιωρούμενα στερεά (TSS) καθώς και των λοιπών φυσικοχημικών παραμέτρων τους. Επιπλέον, παρουσιάζονται κάποιες προτάσεις για την απορρύπανση των στραγγισμάτων των ΧΥΤΑ που πρέπει να γίνεται πριν από την απόρριψη τους σε οποιαδήποτε περιοχή, όπως προ-επεξεργασία των στραγγισμάτων με ένα συνδυασμό φυσικοχημικών, αναερόβιων και υδρολυτικών διαδικασιών. Για την απομάκρυνση βαρέων μετάλλων (όπως Fe, Cd, Cr) καθώς και τη μείωση του COD, μπορεί να είναι αποτελεσματική η προ-επεξεργασία με πήξη-κροκίδωση. Στην παρούσα όμως διπλωματική εργασία για τη μείωση του COD χρησιμοποιήθηκε η Φωτοκαταλυτική Διαδικασία Αποδόμησης (Photocatalytic Degradation Process), η οποία περιλαμβάνει φωτοκαταλυτική επεξεργασία με τη χρήση υπεριώδους ακτινοβολίας (UV) και την προσθήκη καταλύτη οξειδίου του τιτανίου (TiO2) στο δείγμα του στραγγίσματος. Ακόμη, εναλλακτικά χρησιμοποιήθηκε η προσρόφηση με εξανθράκωμα (biochar), Σκοπός αυτών των διαδικασιών είναι η απομάκρυνση των ανθεκτικών οργανικών ενώσεων και ο αποχρωματισμός του στραγγίσματος. Με την ολοκλήρωση των διεργασιών ο αποχρωματισμός του στραγγίσματος επιτεύχθηκε με την ετερογενή φωτοκατάλυση και η σχετική μείωση των οργανικών ρύπων με τη χρήση του ροφητικού μέσου biochar. / Leachate from landfills contains complex organic compounds, a fact that makes its effective treatment a matter of crucial importance nowadays. Apart from high quantities of organic material, leachate also contains heavy metals, organic or anorganic chloride salts and various substances which can pollute surface and ground water. As a result, the construction of landfills must include leachate collection and treatment systems, in order to prevent its filtering through ground and underground, and subsequent pollution of streams, small rivers and wells. This thesis presents the characterization of a leachate sample and testes various decontamination techniques, which could to be executed before its disposal in any area. In particular, leachate pre-treatment can be performed with a combination of physical chemical, anaerobe and hydrolytic methods. In order to remove heavy metals (i.e. Fe, Cd, Cr) and reduce COD, pre-treatment can be effective using flocculation-coagulation. In this thesis a Photocatalytic Degradation Process was used to reduce COD, which consists of photocatalytic treatment using UV radiation and adding TiO2 to the leachate sample. Alternatively, adsorption process with biochar was also tested. The purpose of this process is the removal of persistent organic compounds and the discoloration of the leachate. With the completion of the processes the discoloration of the leachate was accomplished using heterogeneous photocatalysis and the relative reduction of organic pollutes using sorption materials (i.e. biochar).

Submitted by Gizele Lima (gizele.lima@inpa.gov.br) on 2017-11-06T13:25:40Z No. of bitstreams: 2 Dissertação ATU (João Dias).pdf: 2653917 bytes, checksum: 705a98764e4682f72753f59cc3866496 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-11-06T13:25:40Z (GMT). No. of bitstreams: 2 Dissertação ATU (João Dias).pdf: 2653917 bytes, checksum: 705a98764e4682f72753f59cc3866496 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-07-28 / Fundação de Amparo à Pesquisa do Estado do Amazonas - FAPEAM / The availability of phosphorus in Amazonian soils limits agricultural activity due to the high affinity of this nutrient with the soil, culminating in the low efficiency of the fertilizers. One of the techniques recently studied to reverse this scenario is the bio-coal, which is attributed to the ability to reduce processes that make phosphorus unavailable and increase its residual effect on the soil. Considering the above, the objective of this work was to verify the influence of doses of bio-carbon on the residual effect of phosphate fertilizer on soil and nutrition and development of Castanheira-do-Brasil seedlings. Considering the above, the objective of this work was to verify the influence of doses of bio-carbon on the residual effect of phosphate fertilizer on soil and nutrition and development of Brazil Nuts seedlings. The experiment was conducted in a greenhouse using a typical Yellow Latosol, in sequence to an experiment, verifying the immediate effect of the biochar and the phosphorus. A completely randomized design was used in a 5 x 2 factorial arrangement, with five doses of bio-carbon (0, 20, 40, 60 and 80 t ha -1 ) and two previously applied phosphorus (0 and 100 mg dm -3 P 2 O 5 ). The seedlings used in the experiment were assigned by Aruanã S.A company at 7 months of age, being standardized by uniformity and vigor. During the experiment, the height of the seedlings, the collection diameter and the number of leaves were evaluated monthly, and the dry matter production of shoots and roots, main root length and total volume of roots. From these data the rate and absolute growth in height and diameter, shoot / root ratio, leaf gain, number of final leaves and the Dickson quality index were calculated. In addition, the levels of macro and micronutrients foliars and soil attributes were evaluated: hydrogen ionic potential, potential acidity, exchangeable aluminum, macro and micronutrient contents and remaining phosphorus. From these, the saturation and sum of bases, saturation by aluminum, the effective and potential CTC were calculated. Regardless of the residual phosphorus, the biochar increased proportionally to the soil bases (K, Ca, Mg) and consequently the sum and base saturation. The biocarbon present in the substrate continued to positively influence the soil attributes after a year and a half of its application. The application of 20 and 40 t ha -1 of biochar in the substrate promoted the best residual effect of the phosphate fertilizer. Residual phosphorus did not influence in a clear way the foliate absorption of K, Ca and Mg. The increase of the biocharous doses in the substrate promoted decreases in the foliar absorption of phosphorus and favored the absorption of micronutrients. Except for the contents of N and Mn, the contents of the other elements are similar to those found in similar works. The presence of residual phosphorus in lower doses of biochar (<40 t ha -1 ) promoted a better monthly development in height of the seedlings and diameter of the collection. The presence of residual phosphorus promoted increases in the height of the Castanhaeira seedlings, however, it did not significantly influence the collection diameter. The doses above 40 t ha -1 of bio-carbon promoted lower leaf gain, higher height-to-diameter ratio, and lower gains of dry biomass of root and shoot. The presence of residual phosphorus did not positively influence these variables. Lower dry matter ratio of aerial part / roots were obtained at doses above 40 t ha -1 of bio-coal. Greater root length was obtained at biocharging doses above 40 t ha -1 , while lower root volume observed at doses below 40 t ha -1 . The highest quality index of dickson seedlings was obtained at doses below 40 t ha -1 of bio-carbon without the presence of residual phosphorus. / A disponibilidade de fósforo em solos da Amazônia limita atividade agrícolas devido a alta afinidade desse nutriente com o solo, culminando na baixa eficiência dos fertilizantes. Uma das técnicas recentimente estudadas para reverter este cenário destaca-se o biocarvão, ao qual atribui-se a capacidade de diminuir processos que indisponibilizam o fósforo e aumentando seu efeito residual no solo. Diante do exposto, o objetivo deste trabalho foi verificar a influência de doses de biocarvão sobre o efeito residual de adubo fosfatado no solo e na nutrição e desenvolvimento de mudas de Castanheira-do-Brasil. Diante do exposto, o objetivo deste trabalho foi verificar a influência de doses de biocarvão sobre o efeito residual de adubo fosfatado no solo e na nutrição e desenvolvimento de mudas de Castanheira-do-Brasil. O experimento foi conduzido em casa de vegetação utilizando-se Latossolo Amarelo típico, em sequência a um experimento verificando o efeito imediato do biocarvão com o fósforo. Utilizou- se delineamento inteiramente casualisado em arranjo fatorial 5 x 2, sendo cinco doses de biocarvão (0, 20, 40, 60 e 80 t ha -1 ) e duas de fósforo anteriormente aplicado (0 e 100 mg dm -3 de P 2 O 5 ). As mudas utilizadas no experimento foram cedidas pela empresa Aruanã S.A com 7 meses de idade sendo padronizadas pela uniformidade e vigor. Ao longo do experimento avaliou-se mensalmente a altura das mudas, o diâmetro de coleto e o número de folhas e posteriormente ao experimento avaliaram-se a produção de matéria seca da parte aérea e das raízes, o comprimento da raiz principal e o volume total de raízes. A partir desses dados calculou-se a taxa e o crescimento absoluto em altura e diâmetro, a relação parte aérea/raiz, o ganho foliar, número de folhas finais e o índice de qualidade de Dickson. Além disso, avaliou-se a os teores de macro e micronutrientes foliares e atributos do solo: potencial hidrogeniônico, acidez potencial, alumínio trocável, teores de macro e micronutrientes e fósforo remanescente. A partir desses calculou-se a saturação e soma de bases, saturação por alumínio, a CTC efetiva e potencial. Independente do fósforo residual, o biocarvão elevou proporcionalmente às bases do solo (K, Ca, Mg) e consequentemente a soma e saturação por bases. O biocarvão presente no substrato continuou influenciando positivamente nos atributos do solo após um ano e meio de sua aplicação. A aplicação de 20 e 40 t ha -1 de biocarvão no substrato promoveu o melhor efeito residual do adubo fosfatado. O fósforo residual não influenciou de maneira clara a absorção folia de K, Ca e Mg. O aumento das doses de biocarvão no substrato promoveu decréscimos na absorção foliar de fósforo e favocereu a absorção dos micronutrientes. Exceto para os teores de N e Mn, os teores dos outros elementos são semelhantes aos encontrados em trabalhos semelhantes. A presença do fósforo residual em doses mais baixas de biocarvão (< 40 t ha -1 ) promoveu melhor desenvolvimento mensal em altura das mudas e diâmetro do coleto. A presença do fósforo residual promoveu incrementos nas alturas das mudas de Castanhaeira, entretanto, não influenciou expressivamente no diâmetro do coleto. As doses acima de 40 t ha -1 de biocarvão promoveram menores ganhos foliares, maior relação altura/diâmetro e menores ganhos de biomassa seca da raíz e da parte aérea. A presença do fósforo residual não influenciou positivamente nessas variáveis. Menor relação matéria seca da parte aérea/ raízes foram obtidas em doses acima de 40 t ha -1 de biocarvão. Obteve-se maior comprimento de raízes em doses de biocarvão acima de 40 t ha -1 , enquanto que menor volume de raízes observado em doses abaixo de 40 t ha -1 . Obteve-se maior índice de qualidade de dickson das mudas nas doses abaixo de 40 t ha -1 de biocarvão sem a presença do fósforo residual.